N-Methyl Piperidinium Chlorochromate Adsorbed on Alumina: A New and Selective Reagent for the Oxidation of Benzylic Alcohols to their Corresponding Carbonyl Compounds

Summary.  N-Methyl piperidinium chlorochromate adsorbed on alumina oxidizes a wide variety of benzylic alcohols to the corresponding carbonyl compounds. Received May 18, 2000. Accepted (revised) July 4, 2000     

A New Chiral Director for the Highly Diastereoselective Borane Reductionof Steroid-20-ones

Summary.  The synthesis of a new chiral boroxazolidine was achieved which was used to control the stereochemistry of the borane reduction of the 20-keto group of steroids. The otherwise hardly accessible 20α-(20S)-alcohol can thus be prepared in a yield of 91%. Received April 10, 2000. Accepted (revised) May 2, 2000     

Synthesis and Biological Activity of Oxidation Products of the Antiprogestine Mifepristone

Summary.  Selenium dioxide oxidation allows the selective introduction of a hydroxyl group at position 6 of the steroid skeleton of the antihormone (11β, 17β)-11-(4-dimethylamino-phenyl)-17-hydroxyl-17-(1-propynyl)-estra-4,9-dien-3-one (mifepristone, RU 486) and leads in a one-step procedure to two diastereomeric oxidation products. Their structure (6α- and 6β-hydroxy-mifepristone) was determined by NMR spectroscopy. The antiprogestinic activity of the oxidation products is comparable to that of mifepristone. Received August 25, 2000. Accepted (revised) October 24, 2000     

An Unusual Photoreaction of 3,4-Di-O-benzyl-hypericin

Summary.  Upon irradiation of 3,4-di-O-benzyl-hypericin and proton sponge (bis-1,8-N,N-dimethylamino-naphthalene) in benzene solution, a stable radical ion pair formed which exhibited an intense absorption band around 800 nm. This was advanced by UV/Vis, NMR, and ESR spectroscopy. In presence of oxygen, irradiation of this photoproduct led to an activated oxygen species which then attacked the proton sponge. Received July 17, 2000. Accepted July 20, 2000     

Chemoselective Preparation of Oximes, Semicarbazones, and Tosylhydrazoneswithout Catalyst and Solvent

Summary.  A simple and versatile method for the synthesis of oximes, semicarbazones, and tosylhydrazones of aldehydes in the presence of ketones without catalyst and solvent is presented. Received June 28, 2000. Accepted (revised) August 25, 2000     

Reaktionen von Siliciummonoxid mit Münzmetallhalogeniden

Summary.  Reaction of solid SiO with CuI, AgI, AgCl, or AgF results in the formation of the silicon tetrahalides SiX ₄ and elemental silver or copper. The crystal structure of SiI₄ was re-determined (Si-I 2.427(2) and 2.416(4) ?).

Received March 2, 2000. Accepted March 10, 2000     

Environmentally Friendly Arylmethylation of Aromatics with Benzyl Halides Using Envirocat EPZ10® as the Catalyst

Summary.  The Friedel-Crafts arylmethylation of aromatics with benzyl halides or bis-(bromomethyl)-benzene in the presence of Envirocat EPZ10? affords selectively para-arylmethylated products in good yields. Isolation of pure products involving an eco-friendly procedure and recyclability of the catalyst are important features of this method. Received January 17, 2000. Accepted (revised) March 2, 2000     

A Sequence of Aldol Condensations and a Michael Addition Giving a Cyclohexenone Ring System

Summary.  The reaction of 1,5-diphenylpentanetrione, 4-chlorobenzaldehyde, and acetone in the presence of methylamine resulted in 2,6-dibenzoyl-5-(4-chlorphenyl)-3-methyl-cyclohex-2-en-1-one, which was formed by a sequence of a Knoevenagel reaction, an aldol condensation, and a Michael addition in a one-pot reaction. Received August 16, 2000. Accepted September 8, 2000     

A Cyclic Voltammetric Study of Some Porphyrazines

Summary.  Some porphyrazines with dimethylamino- or trimethylammoniumethylsulfanyl substituents were studied in dichloromethane or dimethylsulfoxide solution by cyclic voltammetric methods. The cyclic voltammogram of metal free octakis-(dimethyl-aminoethylsulfanyl)-porphyrazine is characterized by three one-electron reduction waves which show quasi-reversible behaviour at all sweep rates observed; the same holds for its cobalt(II) derivative. The quaternized octacationic derivative, however, exhibits four one-electron reduction waves which are reversible at all sweep rates. The reaction mechanisms and diffusion coefficients were investigated. Received October 17, 2000. Accepted (revised) December 11, 2000     

Synthesis of 2H-Thiopyrans by Rhodium(II) Acetate-Catalyzed Reaction of 4-Amino-2,5-dihydro-3-thiophenecarbonitriles with a-Diazocarbonyl Compounds II [1]

Summary.  The reaction of 4-amino-2,5-dihydro-2- and -5-methyl-3-thiophenecarbonitriles with α-diazocarbonyl compounds in the presence of rhodium(II) acetate gave regioselectively 4-cyano-2H-thiopyrans (C₂-S insertion) in moderate to good yields; 5-cyano-2H-thiopyrans (C₅-S insertion) were not isolated. The starting compounds were synthesized by reaction of tetrahydro-2- and -5-methyl-4-oxo-3-thiophenecarbonitriles with morpholine, piperidine, and pyrrolidine in the presence of formic acid in ethanol. Received November 13, 2000. Accepted December 12, 2000     

Synthesis and Structural Studies of Some β-Diketone Phenylhydrazones and their Complexes with Co(II), Ni(II), and Cu(II)

Summary.  New β-diketone phenylhydrazones prepared by condensation of substituted 3-arylidene-2,4-pentanediones with phenylhydrazine, have been characterized by their elemental analyses, IR, ¹H NMR, and mass spectra. Some complexes of these Schiff bases with Co(II), Ni(II), and Cu(II) ions have been synthesized; in addition to the above methods, their structures were studied by magnetic susceptibility and thermogravimetry measurements. Received January 26, 2000. Accepted (revised) April 14, 2000     

Dynamic 1H NMR Study of Aryl-Nitrogen Single Bond and Carbon-Carbon Double Bond Rotational Energy Barriers in Two Highly Functionalized Pyranopyrimidines

Summary.  The reactive 1:1 intermediate produced in the reaction between 2,6-dimethylphenyl isocyanide and dimethyl acetylenedicarboxylate was trapped by N,N′ -dimethylbarbituric acid to yield the isomeric products dimethyl 7-(2,6-dimethylphenylamino)-1,3-dimethyl-2,4-dioxo-4H-pyrano[3,2-d]pyrimidine-5,6-dicarboxylate and dimethyl (E)-2-((2,6-dimethylphenylamino)-(1,3-dimethyl-2,4,6-trioxo-pyrimidine-5-ylidene)-methyl)-but-2-enedioate in a nearly 1:1 ratio and an overall yield of 85%. Dynamic effects were observed in the ¹H NMR spectra of these compounds and were attributed to restricted rotation around the aryl-nitrogen single bonds and the polarized carbon-carbon double bond. Received September 18, 2000. Accepted (revised) November 22, 2000     

Visible Photoluminescence in Polysilanes

Summary.  The photoluminescence spectrum of poly-(methyl-(phenyl)-silanediyl) shows a strong narrow peak in the UV region which is of excitonic nature and related to σ^*-σ transitions. The broad emission peak in the visible region is related to polymer branching, charge transfer transitions, and defect electronic states (backbone scission). Chemical substitution of the Si backbone with π-conjugated side groups allows to generate photoluminescence also in the visible region. Received June 23, 2000. Accepted (revised) August 7, 2000     

Novel Functional Fullerene Materials: Fullerenes as Energy Acceptors

Summary.  Fullerene derivatives exhibit absorption throughout the UV/Vis region up to 750 nm. This feature is important for easy excitation. Once excited, fullerenes may become both electron and energy acceptors. The distinction between these two pathways depends strongly on the partner involved (donor) and on the conditions employed (solvent, etc.). Received June 23, 2000. Accepted July 7, 2000     

On the Synthesis and Reactions of Indole-2-carboxylic Acid Hydrazide

Summary.  Indole-2-carboxylic acid hydrazide was prepared and allowed to react with aromatic aldehydes in acidic medium to give the corresponding hydrazone derivatives in good yields. The hydrazones were cyclized to indolo[2,3-d]pyridazine derivatives by refluxing with acetyl chloride. The indole carbohydrazide was converted to 2-triazolylindoles which acted as starting materials for several indole derivatives. A number of new indole derivatives were also prepared and structurally confirmed. Received October 17, 2000. Accepted (revised) December 12, 2000     

1,3-Dipolar Cycloadditions VI [1].Structure and Conformation of Cycloadducts from Reactions of C-Aryl-N-phenylnitrones with Substituted Cinnamic Acid Amides

Summary.  Studies on cycloadditions of C,N-diarylnitrones to cinnamic acid amides were carried out. The diastereoisomeric (I, II) and (in some cases) regioisomeric (III) cycloadducts obtained were characterized by spectroscopic and X-ray data. Conformational studies were carried out by molecular modelling. Received February 8, 2000. Accepted February 18, 2000     

Spectroscopic Study of the Conformation of 2-Anilino-2-ethoxy-3-oxothiobutyric Acid Anilides

Summary.  An NMR study of the equilibriummixture of two conformers of 2-anilino-2-ethoxy-3-oxothiobutyric acid anilides 3 allows to estimate their population ratio in solvents of increasing polarity. X-Ray analysis as well as IR spectroscopy confirmed that the conformer present in the solid state is stabilized by two hydrogen bonds. The structural basis of the second conformer observed in solution is the 1,4-type S⋯O interaction between the sulfur of the thioanilide moiety and the oxygen of the ethoxy group with a distance of 2.878 ?. Received May 29, 2000. Accepted (revised) July 14, 2000     

Reaction of Some Alkenols with Tetrachloromethane

Summary.  The reaction of some alkenols with tetrachloromethane in the presence of a radical initiator was investigated. Regarding the effects of structural features of the starting alkenol (number and position of methyl substituents at the double bond and at the carbinol carbon atom, constitutional relationship between the double bond and the hydroxyl group) there are two possible competing reactions: addition and cyclization. In the case of the simplest alkenols (without substituents and with a more remote double bond) addition occurs; mono- and disubstituted secondary and tertiary Δ⁴- and Δ⁵-alkenols cyclize in high yields to give the corresponding cyclic ethers. Received March 17, 2000. Accepted (revised) May 31, 2000     

Zeolite HY and Silica Gel as New and Efficient Heterogenous Catalysts for the Synthesis of Triarylimidazoles under Microwave Irradiation

Summary.  Zeolite HY and silica gel efficiently catalyzed the three component condensation of benzil, benzaldehyde derivatives, and ammonium acetate under solvent-free conditions and microwave irradiation. Received February 22, 2000. Accepted (revised) March 22, 2000     

Highly Regioregular Poly-3-alkylthiophenes: Influence of the Structure on Photoluminescence

Summary.   A class of regioregular poly-3-alkylthiophenes was synthesized via a new and simple synthetic procedure. These polymers exhibit a regioregularity as high as 95–100% and show different thermal behaviour depending on the length of the side chain. The high conjugation length reached is responsible for a red-orange emission with photoluminescence (PL) quantum efficiencies of about 45% in solution. The study of the PL of spin coated films at different temperatures allows to correlate the PL spectra with the structure of the polymers as detected by XRD. Received June 23, 2000. Accepted (revised) August 21, 2000